EP2757158B1 - Enzymatisches verfahren zur herstellung von estoliden - Google Patents

Enzymatisches verfahren zur herstellung von estoliden Download PDF

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Publication number
EP2757158B1
EP2757158B1 EP11872406.1A EP11872406A EP2757158B1 EP 2757158 B1 EP2757158 B1 EP 2757158B1 EP 11872406 A EP11872406 A EP 11872406A EP 2757158 B1 EP2757158 B1 EP 2757158B1
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Prior art keywords
lipase
process according
immobilized
estolides
stearic acid
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English (en)
French (fr)
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EP2757158A1 (de
EP2757158A4 (de
Inventor
Érika Cristina GONÇALVES AGUIEIRAS
Cláudia DE OLIVEIRA VELOSO
Danielle De Oliveira Rosas
Marta Antunes PEREIRA LANGONE
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Petroleo Brasileiro SA Petrobras
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Petroleo Brasileiro SA Petrobras
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M109/00—Lubricating compositions characterised by the base-material being a compound of unknown or incompletely defined constitution
    • C10M109/02—Reaction products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/2805—Esters used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives

Definitions

  • This invention falls within the field of enzymatic processes for the synthesis of estolides to be used as lubricants. More specifically, this invention is a process for enzymatic synthesis of estolides through the reaction between stearic acid and methyl ricinoleate, in solvent free media using a specific type of immobilized lipase as catalyst.
  • Base oils are the principal constituents in the formulation of lubricating oils and are classified as mineral or synthetic. Mineral oils are obtained by distilling and refining petroleum, whereas synthetics are produced by chemical reactions using various raw materials, in an effort to obtain products with properties suitable to the function of lubricants. Mixtures of base oils and additives are normally used to adjust some properties such as viscosity and stability to oxidation and to prevent the formation of deposits.
  • Estolides constitute a new class of lubricants derived from vegetable oils with excellent low temperature properties, the pour point being one of the best indicators of such properties.
  • Estolides is the generic name used to define linear oligomers of polyesters of fatty acids in which the carboxyl group of a fatty acid binds to the unsaturation site of another fatty acid or in which the hydroxyl of a hydroxylated fatty acid is esterified by the carboxyl group of another fatty acid molecule.
  • These lubricants have been synthesized by polymerizing fatty acids under high temperatures or using mineral acid catalysis.
  • US patent 6,316,649 describes a process for synthesizing esters of estolides through the reaction between oleic acid and saturated fatty acids with 6 to 18 carbon atoms and subsequent reaction with 2-ethylhexanol.
  • Perchloric acid was used as the catalyst, with a reaction temperature ranging from 45° C to 60 ° C.
  • the esters of the estolides obtained exhibited good oxidation stability, a high viscosity index, viscosity compatible with mineral base oils, as well as a low pour point and good degradability.
  • U.S. patent 6,018,063 refers to a family of estolides derived from oleic acid, produced by acid catalysis, and characterized by its superior properties when used as lubricants, such as viscosity (at 40 °C) between 20 cSt and 32 cSt, viscosity index of 150, and pour point of between-30°C and -21°C, among others.
  • viscosity at 40 °C
  • Viscosity index of 150 a viscosity index of 150
  • pour point between-30°C and -21°C
  • JP patent 1016591 describes the synthesis of estolides by means of the hydrolysis of hydroxylated fatty acids present in castor oil, more specifically the ricinoleic acid.
  • the hydrolysis reaction and formation of estolide from castor oil was done using 2% to 15% (m/m) of lipase in 30% to 65% (m/m) of castor oil dispersed in an aqueous solution to obtain estolide conversion greater than 90%.
  • the lipases used are those capable of hydrolyzing ⁇ positions of the fatty acids or a lipase capable of partially hydrolyzing glycerides.
  • JP patent 5211878 describes a procedure for obtaining high reaction rates and a high degree of polymerization of estolides, which are free of dark color, odor and impurities.
  • the estolides were synthesized through ricinoleic acid condensation reactions, using immobilized lipase as the catalyst, by controlling the amount of water in the reaction medium.
  • condensation of ricinoleic acid molecules has the disadvantage of resulting in a hygroscopic product.
  • the estolides it is thus also difficult to maintain the properties of the product for each production.
  • Bodalo et al in Biochemical Engineering Journal, vol. 39, no. 3, pages 450-456 , refer to the synthesis of estolides from ricinoleic acid catalyzed by immobilized lipase in a solvent-free reaction. Similar processes are described by Yoshida et al, in JAOCS, vol. 74, no. 2, pages 261-267 , and by Bodalo et al, in Biochemical Engineering Journal, vol. 44, no. 2-3, pages 214-219 .
  • This invention provides a method for synthesizing estolides through a catalyzed esterification reaction using specific lipases immobilized on macroporous acrylic resins in a solvent-free system as detailed in claim 1.
  • the synthesis of estolides using lipases prevents the degradation of reagents and products, and reduces secondary reactions given that these enzymes act in mild reaction conditions and have high specificity.
  • the use of immobilized lipases permits their later reuse.
  • the purification processes are simpler, since fewer components are present in the reaction medium at the end of the reaction. The elimination of solvents in the production of estolides considerably reduces costs and minimizes environmental impact.
  • This invention is a process for enzymatic synthesis of estolides, comprising the reaction between stearic acid and methyl ricinoleate in a solvent-free medium, using an immobilized lipase as the catalyst, wherein the lipase, which is non-specific for the 1,3-positions of a triglyceride, is a recombinant lipase from Candida antarctica , expressed in Apergillus Niger, and is immobilized on macroporous acrylic resins.
  • This invention is an enzymatic process for synthesizing estolides in a solvent-free medium, the objective of which is to selectively produce lubricants generating a product with a high degree of purity and reduced waste production.
  • the solvent-free system (SLS) combines the specificity of biological catalysis with reduced operating costs due to lower energy consumption during the reaction and treatment of effluents.
  • this invention is a process for synthesizing estolides, via enzymatic catalysis, in a solvent-free medium using an immobilized lipase as the catalyst, wherein the lipase, which is non-specific for the 1,3-positions of a triglyceride, is a recombinant lipase from Candida antarctica , expressed in Apergillus Niger, and is immobilized on macroporous acrylic resins, with said process including the following steps:
  • This process utilizes stearic acid from natural sources, particularly vegetable oils and animal fats.
  • Vegetable oil sources include: cotton seed, coconut, palm, castor, rapeseed, soybean, sunflower seed, and olive oils. Particular mention should be made of cocoa butter and shea butter, which have a high stearic acid content, ranging from 28% to 45%.
  • sources include milk fat (5% to 15% stearic acid), pig fat (approximately 10% stearic acid), and bovine tallow with 15% to 30% stearic acid.
  • methyl ricinoleate useful for this invention are the byproducts of acid transesterification and esterification of castor oil (castor bean biodiesel), as castor oil is roughly 90% made up of ricinoleic acid.
  • the reaction between stearic acid and methyl ricinoleate is an esterification / condensation reaction, the efficiency of the reaction being dependent on the type and concentration of lipase used, the temperature of the reaction medium and the amount of water in the medium.
  • lipases with specificity for hydrolysis of the 1, 3-positions of the triglyceride molecules do not act on the hydroxyl group of hydroxylated fatty acids, which are inefficient in the synthesis of estolides derived from these acids.
  • non-specific lipases for the 1, 3-positions are effective in catalyzing this type of reaction.
  • Lipases obtained from genetically-modified microorganisms are used.
  • the lipase is a recombinant lipase from Candida antarctica , expressed in Aspergillus Niger.
  • the lipase marketed by the Novozymes company as Novozyme 435 can be used.
  • the immobilized lipases useful for the process of this invention are not specific for the 1, 3-positions, and are immobilized on macroporous acrylic resins, especially in concentrations greater than 10,000 U/g.
  • estolides Apart from selecting the lipase, another variable to be observed in the enzymatic synthesis of estolides is the influence of temperature on the enzymatic reaction, as a result of decreased enzyme stability due to thermal deactivation.
  • the ideal working temperature for lipase varies from 70°C to 90°C. At temperatures below 70°C, low consumption of fatty acid molecules is observed, the conversion to estolides being less than 30%.
  • the lipase concentration suitable for the process ranges from 6% to 14% (m/m) relative to the total concentration of reagents. In lipase concentrations below 6% (m/m), the conversion is low, generally below 30%. Enzyme concentrations above 14% (m/m) contain an agglomeration of particles of immobilized lipase, reducing the active sites available for reaction, causing a reduction in yield and conversion.
  • the esterification reaction generates water as a byproduct; however, its presence in the reaction medium adversely affects conversion rates, since when the water content in the reaction mixture increases, the reaction reaches an equilibrium and stops. Therefore, the removal of water produced during the reaction is extremely important for the conversion to be high, above 40%.
  • the removal of water from the reaction medium can be done by means of an adsorbent in concentrations between 4% and 7% (m/m).
  • an adsorbent in concentrations between 4% and 7% (m/m).
  • the following may be cited among the adsorbents useful for this invention: alumina, silica gel, zeolites, preferably molecular sieves, or the application of a 60 Pa (0.6 mbar) vacuum.
  • this invention is an enzymatic process, the objective of which is the synthesis of estolides from the reaction between stearic acid and methyl ricinoleate, using immobilized lipases as the catalyst.
  • the lipase can be recovered by vacuum filtration, using n-hexane as a solvent.
  • methyl ricinoleate in condensation reactions with stearic acid, catalyzed by lipases, creates a biodegradable lubricant of high added value, which expands the application scope of castor oil biodiesel and can lead to its commercially viable production.
  • the following example illustrates the effect of the presence of water in the reaction medium in the conversion of the reaction, through the action of an agent for removing water, in this case a molecular sieve.
  • stearic acid P.A. purity grade
  • Novozyme 435 commercial immobilized lipase
  • 937.5 g of methyl ricinoleate obtained through the transesterification of castor oil
  • 500 mg from a 3A molecular sieve 500 mg from a 3A molecular sieve
  • the following example illustrates the effect of the presence of water in the reaction medium on the conversion of the reaction by removal of water through application of a vacuum.
  • the properties of the final product were evaluated to characterize the biolubricant obtained.
  • the biolubricant obtained showed good viscosity properties, a low pour point and an absence of corrosiveness, as compared to a base oil and a commercial lubricant (Lubrax Unitractor), as shown in Table 2.

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  • Chemical & Material Sciences (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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Claims (13)

  1. Verfahren zur enzymatischen Synthese von Estoliden, umfassend die Reaktion von Stearinsäure und Methylricinoleat in einem lösungsmittelfreien Medium unter Verwendung einer immobilisierten Lipase als Katalysator,
    wobei die Lipase, die nicht spezifisch für die 1,3-Positionen eines Triglycerids ist, eine rekombinante Lipase aus Candida antarctica, exprimiert in Apergillus Niger, ist und auf makroporösen Acrylharzen immobilisiert ist.
  2. Verfahren nach Anspruch 1, umfassend die folgenden Schritte:
    a) Herstellen eines Gemischs aus Stearinsäure und Methylricinoleat in einem Molverhältnis zwischen 2:1 und 1:1 mit Rühren und bei Raumtemperatur;
    b) Hinzufügen des Gemischs zu einem Reaktor, der die immobilisierte Lipase enthält, in einem Verhältnis zwischen 6 % und 14 % (m/m) Lipase bezogen auf die Gesamtkonzentration von Reagenzien mit Rühren und Reflux bei Temperaturen zwischen 70 °C und 90 °C über einen Zeitraum von 24 bis 100 Stunden, wobei die Wasserkonzentration in dem Reaktionsmedium auf weniger als 0,05 Gew.-% gehalten wird, um die Expression der katalytischen Aktivität der Lipase zu gewährleisten; und
    c) Gewinnen der immobilisierten Lipase, indem sie durch Filtration aus dem Reaktionsmedium entfernt wird, wodurch ein Strom erlangt wird, der Estolide in Konzentrationen zwischen 35 % und 25 % (m/m) enthält.
  3. Verfahren nach Anspruch 1 oder 2, wobei die Lipase auf makroporösen Acrylharzen in Konzentrationen größer als 10.000 U/g immobilisiert ist.
  4. Verfahren nach Anspruch 1 oder 2, wobei die Stearinsäure ein Öl pflanzlichen Ursprungs als seine Quelle aufweist.
  5. Verfahren nach Anspruch 4, wobei das Öl pflanzlichen Ursprungs aus Folgenden ausgewählt ist: Baumwollsamen-, Kokosnuss-, Palm-, Rizinussamen-, Raps-, Sojabohnen-, Sonnenblumenkern- und Olivenöl.
  6. Verfahren nach Anspruch 1 oder 2, wobei die Stearinsäure ein tierisches Fett als seine Quelle aufweist.
  7. Verfahren nach Anspruch 6, wobei das tierische Fett aus Folgenden ausgewählt ist: Milchfett, Schweinefett und Rindertalg.
  8. Verfahren nach Anspruch 1 oder 2, wobei die Konzentration von Wasser in dem Reaktionsmedium unter Verwendung des Hinzufügens von Adsorbtionsmitteln zu dem Reaktionsmedium in dem Anteil von 4 % und 7 % (m/m) aufrechterhalten wird.
  9. Verfahren nach Anspruch 8, wobei das Adsorptionsmittel aus Folgenden ausgewählt ist: Aluminiumoxid, Kieselgel, Zeolithen.
  10. Verfahren nach Anspruch 8, wobei das Adsorptionsmittel ein Molekularsieb ist.
  11. Verfahren nach Anspruch 1 oder 2, wobei das Wasser in dem Reaktionsmedium durch Anwenden eines Vakuums bei einem Druck von 60 Pa beibehalten wird.
  12. Verfahren nach Anspruch 1 oder 2, wobei die Lipase durch Vakuumfiltration gewonnen wird.
  13. Verfahren nach Anspruch 1, 2 oder 12, wobei die gewonnene Lipase in Kontakt mit einem Lösungsmittel kommt, das n-Hexan ist.
EP11872406.1A 2011-09-14 2011-09-14 Enzymatisches verfahren zur herstellung von estoliden Active EP2757158B1 (de)

Applications Claiming Priority (1)

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PCT/BR2011/000324 WO2013037017A1 (pt) 2011-09-14 2011-09-14 Processo enzimático para a síntese de estolides

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EP2757158A1 EP2757158A1 (de) 2014-07-23
EP2757158A4 EP2757158A4 (de) 2015-06-24
EP2757158B1 true EP2757158B1 (de) 2019-09-04

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Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201505178D0 (en) 2015-03-26 2015-05-13 Stichting Dienst Landbouwkundi Production of fatty acid estolides
FR3073231B1 (fr) 2017-11-08 2020-07-17 Produits Chimiques Auxiliaires Et De Synthese Procede enzymatique pour la formation d'estolides
CN113604520B (zh) * 2021-07-27 2024-07-09 华南理工大学 一种酶法催化制备天麻素三酯的方法

Family Cites Families (9)

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Publication number Priority date Publication date Assignee Title
JPS6416591A (en) 1987-07-09 1989-01-20 Itoh Oil Mfg Production of castor oil fatty acid estolide
JP3157028B2 (ja) * 1992-02-04 2001-04-16 日本碍子株式会社 リシノール酸からのエストライドの製造方法
JP3157038B2 (ja) * 1992-04-30 2001-04-16 伊藤製油株式会社 エストライドの製造方法
FI95395C (fi) * 1994-09-07 1996-01-25 Raision Tehtaat Oy Ab Entsymaattinen menetelmä synteettisen esterin valmistamiseksi kasviöljystä
US6018063A (en) 1998-11-13 2000-01-25 The United States Of America As Represented By The Secretary Of Agriculture Biodegradable oleic estolide ester base stocks and lubricants
US6316649B1 (en) 1998-11-13 2001-11-13 The United States Of America As Represented By The Secretary Of Agriculture Biodegradable oleic estolide ester having saturated fatty acid end group useful as lubricant base stock
FR2858616B1 (fr) * 2003-08-07 2006-02-17 Aldivia Sa Procede d'estolidation par chauffage dielectrique
ES2300197B1 (es) * 2006-09-15 2009-05-01 Universidad De Barcelona Procedimiento de obtencion de polirricinoleato de poliglicerol.
JP5211878B2 (ja) 2008-06-16 2013-06-12 パナソニック株式会社 誘導加熱調理器

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CABRERA Z ET AL: "Novozym 435 displays very different selectivity compared to lipase from Candida antarctica B adsorbed on other hydrophobic supports", JOURNAL OF MOLECULAR CATALYSIS. B, ENZYMATIC, ELSEVIER, AMSTERDAM, NL, vol. 57, no. 1-4, 1 May 2009 (2009-05-01), pages 171 - 176, XP025991192, ISSN: 1381-1177, [retrieved on 20080830], DOI: 10.1016/J.MOLCATB.2008.08.012 *

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EP2757158A1 (de) 2014-07-23
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US20130102041A1 (en) 2013-04-25

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